2,4,5-trioxo-imidazolidine-3-carboxylic acid amides

ABSTRACT

2,4,5-trioxo-imidazolidine-3-carboxylic acid amides possess plant metabolism influencing properties. They may be used for regulating fruit abscission.

United States Patent [191 Barlocher et a1.

[ 1 June 18, 1974 54 2,4,5-TRIOXO-IMIDAZOLlDlNE-3- CARBOXYLIC ACID AMIDES [75] Inventors: Toni Barlocher, Oberwil, Switzerland; Edith Ebert, Lorrach-Stetten, Germany [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Sept. 13, 1972 [21] Appl. No.:' 288,640

[30] Foreign Application Priority Data Sept. 30,1971 Switzerland 14214/71 [51] Int. Cl .Q C07d 49/30 [58] Field of Search 260/3095 [56] References Cited OTHER PUBLICATIONS Najer et a1., Compt. rend. Vol. 249, pages 2215-2217, (1959) Q46.A14

possess plant metabolism influencing properties. They may be used for regulating fruit abscission.

3 Claims, No Drawings 2,4,5-TRIOXO-lMlDAZOLID1NE-3-CARBOXYL1C AClD AMIDES The new 2,4,5-trioxo-imidazo1idine-3-carboxylic acid amides correspond to the formula wherein R represents an alkyl or alkenyl radical with at most four carbon atoms or a phenyl radical which is optionally substituted by chlorine, nitro, lower alkyl containing at most four carbon atoms, and R represents an alkyl or alkenyl radical with at most four carbon atoms.

By the alkyl radicals in formula are meant methyl,

ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.butyl and tert.butyl. Among these radicals, particulalrly the methyl and ethyl group form the alkyl moiety of a phenyl radical. By alkenyl radicals in formula I are meant straight-chain or branched propenyl or butenyl radicals. The allyl and methallyl radicals are preferred.

The new compounds of the formula 1 may also be termed parabanic acid derivatives. According to the present invention they are manufactured by cyclising a urea of the formula 11 R,NHCONH (11) with an oxalyl halide to give a 2,4,5-trioxoimidazolidine derivative of the formula 111 R1N NH (III) and subsequently reacting this product with an isocyanate of the formula IV R NCO iv) in the presence of an organic base.

R and R in the formulae 11 TO IV have the same meanings as given under formula I.

The reactions are carried out in solvents or diluents which are inert towards the reactants. The reaction temperatures are in the range from 10C to 110C.

The following may be used as solvents or diluents which are inert towards the reactants: aliphatic and aromatic hydrocarbons and halogenated hydrocarbons,

such as benzene, toluene, xylenes, petroleum ether, chlorobenzene, methylene chloride, ethylene chloride,

chloroform, carbon tetrachloride, ethers and ethereal solvents, such as dialkyl ether, dioxan, tetrahydrofuran, and acetonitrile; preferably aromatic hydrocarbons such as benzene and toluene or acetonitrile are used.

The reaction of a urea of the formula 11 with an oxalyl halide may take place in the presence of inorganic bases. An organic base is necessary as initiator for the introduction of the CONHR group. Tertiary amines may be used as organic bases, e.g. trialkylamines, such as triethylamine, trimethylamine, dialkylanilines. pyridine and pyridine bases.

The following Examples will serve to illustrate the invention. Further derivatives of the formula 1 which were manufactured according to the process described in the Examples are to be found in the succeeding Table.

EXAMPLE 1 a. 272.3 g of N-phenylurca are dissolved in 1.5 litres of tetrahydrofuran. The solution is heated to 50C and slowly treated with 171 ml of oxalyl chloride, in the course of which the reaction temperature should not exceed C. Stirring is continued for 1 hour at room temperature and then for 4 hours under reflux. The reaction mixture is evaporated and the residue is recrystallised from isopropanol to give 1-pheny1-2,4,5-trioxoimidazolidine (m.p. 214-216C).

b. 19 g of 1-phenyl-2,4,S-trioxo-imidazolidine are suspended in ml of benzene. Upon addition of 1 1.2

ml of methyl isocyanate and 0.5 ml of triethylamine the mixture is allowed to undergo complete reaction over the course of 12 hours by stirring it at room tempera ture. The reaction mixture is cooled to 10C and the analytically pure precipitated 1-phenyl-3- methylcarbamoyl-2,4,5-trioxo-imidazo1idine is filtered with suction and thoroughly washed with benzene. The product melts at 1 10C. (Compound No. 1).

EXAMPLE 2 a. 23 of sodium are reacted in 400 ml of absolute ethanol to give the sodium alcoholate. 74.1 g of methyl urea are added at room temperature and the mixture is stirred until a clear solution forms. While stirring is continued, 146.14 g of oxalic diethyl ester are slowly added dropwise without external cooling, so that the reaction temperature fluctuates between 2530C. Upon completion of addition, the reaction mixture is stirred for 1 hour at room temperature and 1 10 ml of cone. hydrochloric acid is slowly added dropwise so that the reaction temperature does not exceed 30C. The reaction mixture is stirred for 1 hour, then filtered. The filtrate is concentrated until a slurry substance is obtained which is filtered with suction and dried at 50C. The resulting l-methyl-2 ,4,5-trioxoimidazolidine is recrystallised from isopropanol; m.p. 153-154C.'

b. 12.8 g of 1-methyl-2,4,S-trioxo-imidazolidine are suspended in 100 ml of benzene. Upon addition of 12.4 g of allyl isocyanate and 0.5 ml of triethylamine stirring is continued for 2 hours at room temperature and for 4 hours at 40C. Upon cooling, the 1-methy1-3- allylcarbamoyl-Z,4,5-trioxo-imiazolidine is filtered with suction and carefully washed with benzene. After recrystallisation from chloroform the product melts at l06l 10C (compound No. 2).

The following Table lists further compounds of the formula l which were manufactured by the processes described in the preceding Examples.

Compound No. Melting point 129 (deoomp).

See. butyl. Eth

The active substances of the formula 1 influence the growth of plant parts above and below the soil in various ways; they are not phytotoxic in conventional ap plication concentrations and have a slight toxicity to warm blooded animals. The active substances do not bring about any morphological changes or damage which might lead to the death of the plant. The compounds are non-mutagenic and their action differs from that of a herbicidal active substance and a fertiliser.

- The new active substances of the formula I influence in particular the vegetative plant growth and fruit development, as well as the development of abscission tissues between stern and leaf or between stem and fruit. It is thereby possible to detach fruit of all kinds, e. g. citrus fruit, stone fruit, pomaceous fruit, nuts, berries, grapes, bananas, pineapples, tomatoes or oleaginous fruit, without applying any great force either manually or with the aid of machines specially developped for the purpose.

The damage which is customarily inflicted on the leaves and branches of the trees and bushes during harvesting by vigorously shaking them, as well as by plucking the fruit, is very largely avoided.

On the other hand, by applying the active substances in a specific concentration it is also possible to provoke leaf shedding in certain cultivated plants, such as cotton, soya, ornamental bushes, green beans and green peas, a factor which is also of economic importance. Tests also proved that a thinning out of blossom and fruit occurs in fruit trees.

LII

' caused to the leaves of the plants. This is of practical importance, for example, in combating undesirable side-shoots in tobacco plants. Experience proves that it is necessary to sever or remove these side-shoots in order to avoid loss of quality or quantity in the leaf yield. Various ornamental plants, e.g. azaleas and chrysanthemums are pruned by hand, i.e., the leading shoot is cut off or pruned in order that the plant may branch. The cited compounds can also be used for this purpose in order to inhibit or kill the still young terminal buds.

The extent and nature of the action are dependent upon the most diverse factors which vary from one kind of plant to another, in particular on the application concentration, the time of application with regard to the development stage of the plant, and on the fruit. Thus, for example, plants whose fruit is utilised or processed are treated immediately after blossoming or at an appropriate interval of time before harvesting.

The active substances are applied in the form of solid or liquid agents both on parts of plants above the soil and in or on the soil. Application to parts of plants above the soil is preferred, for which purpose solutions or aqueous dispersions are best suited. Besides solutions and dispersions, dusts, granules and tracking agents are also suitable for the treatment of the soil.

Analogous Test l Abscission of Fruit In Florida, single branches of citrus trees of the indicated variety and which carried at least 12-50 ripe fruit, were sprayed with active substance concentra tions of 0.4 percent and 0.2 percent. Seven days after the application the plucking force of 10 similarly treated fruit was determined with the aid of a spring balance and the mean value calculated from the 10 measurements (W. C. Wilson and C. H. Hendershott. Proc. Am. Soc. Hort. Science 90, i23-l25 (1967)]. The active substances of the formula I in this test effected the reductions in plucking forms reproduced in the following Table. Two varieties of orange were used for the test:

1 Valencia The fruit hanging on the tree as so easily detached that no measurement was possible.

The fruit in all cases displayed no signs of damage; also no leaves and no green fruit were detached.

Biologial Test ll Test as Preservatives for Cut Flowers Roses of the variety Dr. Verhagen (Holland) were used as test flowers. They were placed in the respective test solutions and kept in a conditioning cabinet of constant temperature (about C) and at a relative humidity of about 80 percent. Their condition was checked each day. The Table indicates how many days the blossoms remained durable without losing petals or displaying signs of withering.

The avtice substances were not tested direct in water, but in a stock solution buffered to pH 3.4 which contained lrgasan as fungicide. These roses were in each container and three containers in each case contained the same solution. The durability in the stock solution containing no active substances is given as comparison. The active substances were added on a rule in a concentration of 50 ppm'and formulated as wettable powders.

Conc. Durability 2,4.5-trioxo-imidazolidinc Control: H O (pH 3.4+fungicide) The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may be available and can be used in the following forms:

Solid forms:

dusts, tracking agents, granules, coated granules,

impregnated granules and homogeneous granules. Liquid a. active substances which are dipersible in water: wettable powders, pastes, emulsions;

b. solutions.

To manufacture. solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one another.

The particle size of the carriers for dusts is advantageously up to about 01 mm, for tracking agents from about 0.075 to 0.2 mm, and for granules 0.2 mm or larger. The concentrations of active substance in the solid forms are from 0.5 percent to percent.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols havingS to 15 ethylene oxide radicals per molecule and eight to nine carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and eight to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde. and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water in any concentration desired. They consistof active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, optionally solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used,

for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfonated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetal ene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are so mixed, ground sieved and strained with the additives mentioned above that, in wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes, of 0.03 is not exceded. To produce emulsifiable concentrates and pastes, dispersing agents such as those given in the previous paragraphs, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xy-

lenes, toluene, dimethyl sulfoxide, N,N -dialkylated amides, N-oxides of amines, especially trialkylamines, and mineral oil fractions boiling between 120 and 350C. The solvents must be practically odorless, not phytotoxic, inert to the active substances and not readily inflammable.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substances or several active substances are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes and mineral oils alone or mixed with each other, can be used as organic solvents. The solutions should contain the active substances in a concentration ranging from 1 percent to 20 percent. These solutions may be applied either with the aid of a propellant gas (as spray) or with special sprayers (as aerosol). The agents described according to the invention can be mixed with other biocidally active substances or agents. Thus in order to broaden the activity spectrum the new agents may contain, for example insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematocides,

in addition to the cited compounds of formula I. The

agents according to the invention may also contain plant fertilizers, trace elements etc.

The active substances of-the formula 1 can, for example, be formulated as follows. The parts denote parts by parts of kaolin (particle size: 0.3-0.8 mm) The active substance is mixed with epichlorohydrin and the mixture dissolved in 6 parts of acetone, then polyethylene glycol ether and cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin and then evaporated in vacuo.

Wettable' Powder,

The following constituents are used to manufacture (a) a 40 (b) a 50 (c) a 25 and (d) a 10 wettable powder:

(a) 40 parts of 1-mcthyl-3-allylcarbamoyl2,4.S-trioxo-imidazolidine 5 parts of sodium lignin sulphonate 1 part of sodium dibutylnapthalenesulphonate 54 parts of silicic acid (b) 50 parts of l-mcthyl-3-methylcarbamoyl-2,4.5-trioxo-imidazolidine 5 parts of alkylarylsulphonate (Tinovetin B") 10 parts of calcium lignin sulphonate 1 part of Champagne chalklhydroxyethyl cellulose mixture (1:1) 20 parts of silicic acid 14 parts of kaolin (c) 25 parts of The active substances are intimately mixed in suitable mixers with the additives and ground in appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration. These suspensions can be used e.g. for removing undesirable side-shoots, for the tillering of grass or for the rooting of cuttings.

Emulsion Concentrate To manufacture 25 7r emulsion concentrates parts of l-ethyl3 n butylcarbamoylQ,4,5-trioxo-imidazolidme 5 parts of a mixture of nonylphenolpolyoxyethylene and calcium dodecylbenzenesulphonate parts of xylene (b) 25 parts of l-phcnyl-3-meth lcarbamoy|-2.4.5-trioxo-imidazolirline 10 parts of a mixture of nonylphcnolpolyoxyethylene and calcium dodecylhenzcnesulphonatc 65 parts of cyclohexanone are mixed together. This concentrate can be diluted with water to suitable concentrations. These emulsions are suitable for thinning out blossoms and fruit, for accelerating the ripening of fruit and for promoting the detachment of fruit and leaves.

We claim:

I. A 2,4,5-trioxo-imidazolidine-3-carboxylic acid amide of the formula 1 wherein R represents alkyl or alkenyl each of up to four carbon atoms or phenyl optionally substituted by chlorine, nitro, or alkyl of l4 carbon atoms, and R represents alkyl or alkenyl each of up to four carbon atoms.

2. A 2,4,5-trioxo-imidazolidine-3-carboxylic acid amide according to claim 1, wherein R represents methyl, ethyl, isopropyl, sec.butyl, allyl, or phenyl optionally substituted by chlorine, nitro, methyl or ethyl, and R represents alkyl of 14 carbon atoms or allyl.

3. l-methyl-2,4,S-trioxo-imidazolidine-3-carboxylicacid-n-propylamide according to claim 1. 

2. A 2,4,5-trioxo-imidazolidine-3-carboxylic acid amide according to claim 1, wherein R1 represents methyl, ethyl, isopropyl, sec.butyl, allyl, or phenyl optionally substituted by chlorine, nitro, methyl or ethyl, and R2 represents alkyl of 1-4 carbon atoms or allyl.
 3. 1-methyl-2,4,5-trioxo-imidazolidine-3-carboxylic-acid-n-propylamide according to claim
 1. 